CN113731195B - Synthesis method and application of mixed metal organic framework film - Google Patents
Synthesis method and application of mixed metal organic framework film Download PDFInfo
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- CN113731195B CN113731195B CN202110991613.6A CN202110991613A CN113731195B CN 113731195 B CN113731195 B CN 113731195B CN 202110991613 A CN202110991613 A CN 202110991613A CN 113731195 B CN113731195 B CN 113731195B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 95
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000011701 zinc Substances 0.000 claims description 46
- 229910052725 zinc Inorganic materials 0.000 claims description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 25
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- -1 N-diethylformamide Chemical compound 0.000 claims description 20
- 239000013110 organic ligand Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- FHZALEJIENDROK-UHFFFAOYSA-N 5-bromo-1h-imidazole Chemical compound BrC1=CN=CN1 FHZALEJIENDROK-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000010408 film Substances 0.000 abstract description 49
- 239000011159 matrix material Substances 0.000 abstract description 42
- 230000004907 flux Effects 0.000 abstract description 10
- 239000012920 MOF membrane Substances 0.000 abstract description 5
- 239000012923 MOF film Substances 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 48
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 48
- 239000013177 MIL-101 Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 18
- 239000013207 UiO-66 Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004246 zinc acetate Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004941 mixed matrix membrane Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the field of novel functional materials, and discloses a synthesis method and application of a mixed metal organic framework film. The design idea of the synthesis method of the invention is as follows: firstly synthesizing metal organic framework particles, then uniformly dispersing the metal organic framework particles in the multifunctional metal gel, and forming the mixed metal organic framework film after heating treatment. According to the invention, the MOF film is used as a continuous phase matrix, and the MOF particles with higher specific surface area or larger aperture are doped to be used as a disperse phase, so that the novel mixed metal organic framework matrix film is constructed. The addition of metal organic framework particles not only can increase the permeation flux and selectivity of the MOF membrane, but also can provide more heterogeneous nucleation sites for the growth of the membrane and promote the continuity of the membrane. Therefore, the method can be well applied to gas separation and purification.
Description
Technical Field
The invention belongs to the field of novel functional materials, and particularly relates to a synthesis method and application of a mixed metal organic framework film.
Background
Membrane separation has attracted great interest in purification and separation due to its environmental friendliness, convenience in process and low energy consumption. As a separation membrane developed in the earliest stage, the polymer membrane has the advantages of low cost, easy processing, easy filling and the like. The polymer film is typically made of an organic polymer. However, conventional polymer membranes are affected by the "upper roberson limit" between selectivity and permeability, and high flux and high selectivity cannot be obtained at the same time, which hinders their further application. To improve the separation performance of polymer membranes, porous materials such as zeolite molecular sieves, covalent organic framework materials, and the like are added to the polymer matrix to construct Mixed Matrix Membranes (MMMs). Among the numerous nanoporous materials, metal Organic Frameworks (MOFs) are receiving great attention due to their highly diverse structures, regular pore channels, and functionalization. However, the performance of MMMs is greatly limited by the properties of the polymer. In general, the loading of filler in MMMs is typically limited to below 40wt%, and too high loading can lead to particle agglomeration and sedimentation, thereby reducing the separation performance of the membrane.
Compared with the mixed matrix membrane, the MOFs and the MOFs have better compatibility, a membrane penetrated by particles can be constructed, the formation of phase interface defects is avoided as much as possible, and meanwhile, the MOF membrane shows higher permeation flux. Methods of constructing conventional MOF films can be divided into two types, depending on the precursor phase, including solution methods and vapor deposition methods. The solution process typically involves impregnating a porous substrate into a precursor mixture or interface by heterogeneous crystallization to assemble a continuous MOF layer. The vapor deposition method mainly builds a continuous MOF film by vapor deposition reaction of metal precursors and organic ligands. The solution method is difficult to add nano/micro particles before film formation and form a composite layer with excellent dispersibility as in MMMs preparation; meanwhile, the method involves the problems of competition of homogeneous/heterogeneous crystallization, large solvent consumption and the like. Vapor deposition methods also involve molecular structured assembly and are difficult to simply use for mixed metal organic framework film construction. Therefore, the existing metal organic framework membrane preparation method at present cannot introduce heterogeneous MOF particles while obtaining a continuous MOF membrane so as to improve the separation performance of the membrane. Therefore, the method for synthesizing the novel mixed metal organic framework membrane is explored and developed, and has important significance for industrial preparation and practical application of the metal organic framework membrane.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a method for synthesizing a mixed metal organic framework membrane. The design idea of the synthesis method of the invention is as follows: firstly synthesizing metal organic framework particles, then uniformly dispersing the metal organic framework particles in the multifunctional metal gel, and forming the mixed metal organic framework film after heating treatment. The addition of metal-organic framework particles not only can provide more heterogeneous nucleation sites for the growth of metal-organic framework films, but also can provide transport channels for gas molecules.
Another object of the present invention is to provide a mixed metal organic framework film synthesized by the above method.
It is a further object of the present invention to provide the use of the above mixed metal organic framework membrane.
The aim of the invention is achieved by the following scheme:
the synthesis method of the mixed metal organic framework film comprises the following steps:
(1) Preparing metal organic framework particles: adding metal salt A and organic ligand A into solvent A, mixing uniformly to obtain synthetic solution, carrying out solvothermal reaction on the synthetic solution, naturally cooling after the reaction is finished, washing and drying to obtain metal-organic framework particles;
(2) Preparing mixed metal gel: adding metal salt B into a solvent B, stirring and dispersing uniformly at 30-80 ℃, then adding a chelating agent, continuing stirring and reacting for 10-80 min at constant temperature to obtain metal sol, adding metal organic framework particles into the obtained metal sol, uniformly mixing, cooling to room temperature, adding an organic ligand B, and stirring uniformly to obtain mixed metal gel containing the metal organic framework particles;
(3) Synthesizing a mixed metal organic framework film: and (3) coating the mixed metal gel containing the metal-organic framework particles obtained in the step (2) on a substrate, then carrying out heat treatment at 60-250 ℃ for 12-48h, naturally cooling to room temperature, taking out the synthesized film, soaking the synthesized film in a solvent C, and drying to obtain the mixed metal-organic framework film.
The metal element in the metal salt A in the step (1) is one of Zn, al, fe, cu, ti, cr, co, ni, mg, zr, nb, mo, mn, sm, gd; the metal salt a is usually a nitrate, chloride, carbonate, sulfate or acetate of a metal, and particularly preferably one of zinc nitrate, cobalt nitrate, zinc acetate, copper chloride, zinc chloride, aluminum chloride, copper nitrate, and zirconium chloride.
The organic ligand A in the step (1) is one of 2-imidazole formaldehyde, 2-methylimidazole, 4-bromoimidazole, imidazole, benzimidazole, terephthalic acid, trimesic acid, 2-amino terephthalic acid and 1, 4-phthalic acid;
the ratio of the amount of the metal salt A to the organic ligand A in the step (1) is 1:0.5-8 (preferably 1:1-2);
the solvent A in the step (1) is one of a solvent D, a mixed solution of the solvent D and water and a mixed solution of hydrofluoric acid and water, wherein the solvent D is at least one of methanol, N-dimethylacetamide, N-diethylformamide, N-dimethylformamide, octanol and ethanol; the solvent A is only used as a reaction medium and does not participate in the reaction, so that the dosage is not required to be limited; preferably 4000 to 110000mL of solvent A is used per 1mol of metal salt A, more preferably 6000 to 50000mL of solvent A is used per 1mol of metal salt A;
the solvothermal reaction in the step (1) is heat treatment for 6-72 hours at 40-300 ℃ in a stainless steel autoclave lined with polytetrafluoroethylene.
The washing in the step (1) is preferably performed with at least one of a solvent D, a mixture of the solvent D and water, and a mixture of hydrofluoric acid and water, wherein the solvent D is at least one of methanol, N-dimethylacetamide, N-diethylformamide, N-dimethylformamide, octanol, and ethanol.
The metal element in the metal salt B in the step (2) is one of Zn, al, fe, cu, ti, cr, co, ni, mg, zr, nb, mo, mn, sm, gd; the metal salt B is usually a nitrate, chloride, carbonate, sulfate or acetate of a metal, and specifically preferably one of zinc nitrate, cobalt nitrate, zinc acetate, copper chloride, zinc chloride, aluminum chloride, copper nitrate, and zirconium chloride.
The solvent B in the step (2) is monohydric alcohol, dihydric alcohol and alcohol derivatives, preferably one of ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, ethylene glycol ethyl ether or ethylene glycol methyl ether; the volume amount of the solvent B is 0.5-50 mL/g (preferably 2-22 mL/g) based on the mass of the metal salt B.
The chelating agent in the step (2) is one of ethanolamine, ethylenediamine, diethanolamine, triethanolamine, 2-aminoethanol, triethylamine, diethylenetriamine or ammonia water, preferably one of ethylenediamine, ethanolamine or ammonia water; the ratio of the chelating agent to the metal salt B is 1:0.5-8 (preferably 1:1-3);
the organic ligand B in the step (2) is at least one of 2-imidazole formaldehyde, 2-methylimidazole, 4-bromoimidazole, imidazole, benzimidazole, terephthalic acid and trimesic acid; the ratio of the amounts of the metal salt B to the organic ligand B is 1:0.5 to 12 (preferably 1:1 to 5).
The metal-organic framework particles in the step (2) are at least one of the metal-organic framework particles prepared in the step (1).
The ratio of the amount of the metal-organic framework particles in the step (2) to the mass of the metal-organic framework material formed by the metal gel is 0-50% (preferably 0-20%).
The substrate in the step (3) is in a flat plate type, a tubular type or a hollow fiber type; the substrate in the step (3) is made of polypropylene, polyethylene, alumina, titanium dioxide, copper, polytetrafluoroethylene, polyimide, polyether ether ketone, polyvinylidene fluoride, polyacrylonitrile, polysulfone, polyether sulfone, cellulose or zinc, preferably polysulfone, polyether sulfone, anodized aluminum, polyacrylonitrile, polyvinylidene fluoride, polyetherimide or polyacrylonitrile.
In the step (3), the solvent C is at least one of methanol, N-dimethylacetamide, N-diethylformamide, N-dimethylformamide, octanol and ethanol.
A mixed metal organic framework film prepared by the method.
The application of the mixed metal organic framework membrane in gas separation and purification.
Compared with the prior art, the invention has the following advantages:
(1) MOF membrane is used as continuous phase matrix, MOF particles with higher specific surface area or larger aperture are doped as disperse phase, and a novel mixed metal organic framework matrix membrane is constructed.
(2) The addition of metal organic framework particles not only can increase the permeation flux and selectivity of the MOF membrane, but also can provide more heterogeneous nucleation sites for the growth of the membrane and promote the continuity of the membrane.
(3) The method has wide universality, can be suitable for constructing various mixed metal organic framework films, and has good application value and prospect.
Drawings
FIG. 1 shows the UiO-66-NH produced in example 1 of the present invention 2 SEM images of the mixed ZIF-8 matrix membrane, where (a) is the membrane surface and (b) is the cross section;
FIG. 2 is a diagram of UiO-66-NH prepared in example 1 2 Mixed ZIF-8 matrix membranes, uiO-66-NH 2 And XRD patterns of ZIF-8 prepared in comparative examples; wherein ZIF-8 represents the ZIF-8 membrane prepared in comparative example 1, U N Z-M 5 Represents UiO-66-NH 2 Mixing ZIF-8 matrix membranes;
FIG. 3 is a diagram of UiO-66-NH prepared in example 1 of the present invention 2 Gas flux comparison plots of the mixed ZIF-8 matrix membranes and the ZIF-8 membranes prepared in the comparative examples. Wherein ZIF-8 represents the flux of the ZIF-8 membrane prepared in comparative example 1, U N Z-M 5 Represents UiO-66-NH 2 Mixing the flux of the ZIF-8 matrix membrane;
FIG. 4 is an SEM image of a MIL-101 mixed ZIF-8 matrix membrane prepared in example 2 of the present invention, where (a) is the membrane surface and (b) is the cross-section;
FIG. 5 is an SEM image of a UiO-66 mixed ZIF-8 matrix membrane prepared in example 3 of the present invention, where (a) is the membrane surface and (b) is the cross-section;
FIG. 6 is an SEM image of a ZIF-8 film prepared in a comparative example of the present invention, where (a) is the film surface and (b) is the cross section.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present invention, the terms "metal salt a" and "metal salt B" have no particular meaning, and all refer to metal salts in the general sense, and the labels "a" and "B" are used only to distinguish metal salts used in different steps. The terms "organic ligand a", "organic ligand B", "solvent a", "solvent B", "solvent C", "solvent D" are the same.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
MOF particles are UiO-66-NH 2 The metal gel is zinc gel, the substrate is anodic aluminum oxide substrate (AAO), and the synthesized mixed metal organic framework film is UIO-66-NH 2 The ZIF-8 matrix membrane was mixed.
The preparation method comprises the following steps:
(1)UiO-66-NH 2 is prepared from the following steps: uiO-66-NH 2 Prepared by solvothermal synthesis. Zirconium chloride (0.48 g) and 2-amino terephthalic acid (0.372 g) were dissolved in N, N-dimethylformamide (40 mL) and water (0.19 mL) by stirring and sonication. The solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 120 ℃ for 24 hours. After natural cooling, the powder was isolated by centrifugation at 6000rpm for 5 min. Finally, the powder obtained is washed several times with N, N-dimethylformamide and methanol.
(2) Preparation of a catalyst containing UiO-66-NH 2 Is a gel of (a): zinc acetate (3.467 g) is added into ethanol (10 mL), stirred at a constant temperature of 60 ℃ for 20min, then ethanolamine (1.0 mL) is added into the solution, stirred at a constant temperature of 60 ℃ for 20min for reaction, transparent zinc sol is obtained, and the solution is cooled to room temperature for standby. UiO-66-NH 2 (0.0327 g) is added into 1mL zinc sol, ultrasonic treated for 5min, stirred for 5min, and circulated for three times to obtain UiO-66-NH 2 Uniformly dispersed in zinc sol. After uniform dispersion, 2-methylimidazole (0.519 g) was added to the sol and stirred rapidly for several minutes to give a solution containing UiO-66-NH 2 Is a zinc gel of (a).
(3) Synthesis of UiO-66-NH 2 Mixing ZIF-8 matrix film: taking the UiO-66-NH containing product obtained in the step (2) 2 Spin-coating zinc gel of the particles on an AAO substrate, drying at 120 ℃ for 25 hours, taking out the synthesized mixed metal skeleton membrane after the reaction system is naturally cooled, soaking the mixed metal skeleton membrane with solvent methanol for 2 hours, and drying the mixed metal skeleton membrane for 24 hours in the methanol atmosphere to obtain the UiO-66-NH 2 Mixed ZIF-8 matrix membranes (SEM image of FIG. 1) described as UiO-66-NH 2 The mass fraction of ZIF-8 is 10wt% (namely UIO-66-NH) 2 The mass ratio of ZIF-8 formed with zinc gel was 10%).
As in figure 2 XRD pattern (whichMiddle U N Z-M 5 Represents UiO-66-NH 2 Mixed ZIF-8 matrix membrane), the obtained UiO-66-NH 2 The XRD pattern of the mixed ZIF-8 matrix film was similar to that of the ZIF-8 film prepared in comparative example 1 and UiO-66-NH was present 2 Shows that UiO-66-NH was successfully prepared under experimental conditions 2 The ZIF-8 matrix membrane was mixed. Simultaneously, uiO-66-NH is subjected to constant pressure capacitance-variable method 2 Single component gas separation performance characterization of mixed ZIF-8 matrix membranes, experimental results are shown in FIG. 3, and compared with the original ZIF-8 membrane of comparative example 1, UIO-66-NH 2 The permeation of hydrogen, carbon dioxide, nitrogen, methane and propane of the mixed ZIF-8 matrix membrane is obviously increased, wherein the permeation flux of hydrogen is improved from 1925Barrer to 3349Barrer, which indicates that the permeation flux of the mixed metal organic framework membrane can be enhanced by adding metal organic framework particles. And the gas fluxes are different, uiO-66-NH 2 The mixed ZIF-8 matrix membrane shows good separation performance, which shows that the prepared UiO-66-NH 2 The mixed ZIF-8 matrix film is continuous and compact, and has no obvious defect.
Example 2
MOF particles are MIL-101, metal gel is zinc gel, a substrate is an anodic aluminum oxide substrate (AAO), and the synthesized mixed metal organic framework membrane is a MIL-101 mixed ZIF-8 matrix membrane.
The preparation method comprises the following steps:
(1) Preparation of MIL-101: chromium nitrate nonahydrate (1.2 g), 1, 4-phthalic acid (0.5 g) and hydrofluoric acid solution (0.6 mL) were added to deionized water (15.0 mL) and stirred for 10min. The mixture was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 220 ℃ for 8 hours. After crystallization, MILs-101 powder was separated by centrifugation and washed.
(2) Preparing zinc gel containing MIL-101: zinc acetate (3.467 g) is added into ethanol (10 mL), stirred at a constant temperature of 60 ℃ for 20min, then ethanolamine (1.0 mL) is added into the solution, stirred at a constant temperature of 60 ℃ for 20min for reaction, and transparent non-precipitate zinc sol is obtained and cooled to room temperature for standby. MIL-101 (0.0327 g) was added to 1mL of zinc sol, sonicated for 5min, stirred for 5min, and cycled three times to allow MIL-101 to disperse uniformly in the zinc sol. After uniform dispersion, 2-methylimidazole (0.519 g) was added and stirred rapidly for several minutes to give a zinc gel containing MIL-101.
(3) Synthesis of MIL-101 Mixed ZIF-8 matrix Membrane: and (2) spinning 200uL of zinc gel containing MIL-101 particles obtained in the step (2) on an AAO substrate, drying at 120 ℃ for 25 hours, naturally cooling a reaction system, taking out a synthesized film, soaking the film in solvent methanol for 2 hours, and drying the film for 24 hours in a methanol atmosphere to obtain the MIL-101 mixed ZIF-8 matrix film (an SEM image of the MIL-101 mixed ZIF-8 matrix film is shown in fig. 4), wherein the mass fraction of MIL-101 to ZIF-8 is 10wt% (namely, the mass ratio of MIL-101 to ZIF-8 generated by zinc gel is 10%).
Example 3
The MOF particles are UiO-66, the metal gel is zinc gel, the substrate is an anodic aluminum oxide substrate (AAO), and the synthesized metal-organic framework mixed metal-organic framework matrix film is a UiO-66 mixed ZIF-8 matrix film.
The preparation method comprises the following steps:
(1) Preparation of UiO-66: zirconium chloride (0.53 g), terephthalic acid (0.3467 g) were added to N, N-dimethylformamide (31.5 mL) by stirring and sonication. The solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 120 ℃ for 24 hours. After natural cooling, the UiO-66 powder was isolated and washed several times with N, N-dimethylformamide and methanol.
(2) Preparation of zinc gel containing UiO-66: zinc acetate (3.467 g) is added into ethanol (10 mL), stirred at a constant temperature of 60 ℃ for 20min, then ethanolamine (1.0 mL) is added, stirred at a constant temperature of 60 ℃ for 20min for reaction, and transparent non-precipitate zinc sol is obtained and cooled to room temperature for standby. UiO-66 (0.1308 g) was added to 1mL of zinc sol, sonicated for 5min, stirred for 5min, and cycled three times to allow uniform dispersion of UiO-66 in the zinc sol. After uniform dispersion, 2-methylimidazole (0.519 g) was added and stirred rapidly for several minutes to give a zinc gel containing UiO-66.
(3) Synthesis of UiO-66 Mixed ZIF-8 matrix Membrane: and (3) spinning 200uL of zinc gel containing UiO-66 particles obtained in the step (2) on an AAO substrate, drying at 120 ℃ for 25 hours, naturally cooling a reaction system, taking out a synthesized film, soaking the film in solvent methanol for 2 hours, and drying the film in a methanol atmosphere for 24 hours to obtain the UiO-66 mixed ZIF-8 matrix film (an SEM image of FIG. 5), wherein the mass fraction of the UiO-66 in the ZIF-8 is 40wt%.
Example 4
MOF particles are UiO-66-NH 2 The metal gel is copper gel, the substrate is Anodic Aluminum Oxide (AAO), and the metal-organic framework mixed metal-organic framework matrix film is UiO-66-NH 2 The CuBTC matrix film was mixed.
The preparation method comprises the following steps:
(1)UiO-66-NH 2 is prepared from the following steps: uiO-66-NH 2 Prepared by solvothermal synthesis. Zirconium chloride (0.48 g) and 2-amino terephthalic acid (0.372 g) were dissolved in N, N-dimethylformamide (40 mL) and water (0.19 mL) by stirring and sonication. The solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 120 ℃ for 24 hours. After natural cooling, the powder was isolated by centrifugation at 6000rpm for 5 min. Finally, the powder obtained is washed several times with N, N-dimethylformamide and methanol.
(2) Preparation of a catalyst containing UiO-66-NH 2 Is a copper gel of (a): copper nitrate trihydrate (3.817 g) is added into ethylene glycol methyl ether (50 mL), stirred at 50 ℃ for 40min, then ammonia water (1 mL) is added, stirred at 50 ℃ for 20min to obtain copper sol, and the copper sol is placed at normal temperature for standby. UiO-66-NH 2 (0.0327 g) was added to 1mL copper sol, sonicated for 5min, stirred for 5min, and cycled three times to give UiO-66-NH 2 Uniformly dispersed in the copper sol. After uniform dispersion, trimesic acid (0.42 g) was added and stirred rapidly for several minutes to give a solution containing UiO-66-NH 2 Is a copper gel of (a).
(3) Synthesis of UiO-66-NH 2 Mixed CuBTC matrix film: taking the UiO-66-NH containing product obtained in the step (2) 2 The granular copper gel 200uL is spin-coated on an AAO substrate, dried at 120 ℃ for 25 hours, and after the reaction system is naturally cooled, the synthesized film is taken out, soaked in solvent methanol for 2 hours and dried for 24 hours in the methanol atmosphere, so as to obtain the UiO-66-NH 2 Mixed CuBTC matrix film, said UiO-66-NH 2 The mass fraction of the CuBTC is 10wt%.
Example 5
MOF particles are UiO-66-NH 2 The metal gel isZinc gel, wherein the substrate is a polyether sulfone hollow fiber membrane, and the synthesized metal-organic framework mixed metal-organic framework matrix membrane is UiO-66-NH 2 The ZIF-67 matrix membrane was mixed.
The preparation method comprises the following steps:
(1)UiO-66-NH 2 is prepared from the following steps: uiO-66-NH 2 Prepared by solvothermal synthesis. Zirconium chloride (0.48 g) and 2-amino terephthalic acid (0.372 g) were dissolved in N, N-dimethylformamide (40 mL) and water (0.19 mL) by stirring and sonication. The solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 120 ℃ for 24 hours. After natural cooling, the powder was isolated by centrifugation at 6000rpm for 5 min. Finally, the powder obtained is washed several times with N, N-dimethylformamide and methanol.
(2) Preparation of a catalyst containing UiO-66-NH 2 Is a gel of (a): zinc acetate (3.467 g) is added into ethanol (10 mL), stirred at a constant temperature of 60 ℃ for 20min, then ethanolamine (1.0 mL) is added into the solution, stirred at a constant temperature of 60 ℃ for 20min for reaction, transparent zinc sol is obtained, and the solution is cooled to room temperature for standby. UiO-66-NH 2 (0.0327 g) is added into 1mL zinc sol, ultrasonic treated for 5min, stirred for 5min, and circulated for three times to obtain UiO-66-NH 2 Uniformly dispersed in zinc sol. After uniform dispersion, 2-methylimidazole (0.519 g) was added to the sol and stirred rapidly for several minutes to give a solution containing UiO-66-NH 2 Is a zinc gel of (a).
(3) Synthesis of UiO-66-NH 2 Mixing ZIF-8 matrix film: soaking 1cm long polyethersulfone hollow fiber membrane in the solution containing UiO-66-NH obtained in step (2) 2 The particles were in zinc gel for 1min and then removed. Drying at 120deg.C for 25h, naturally cooling the reaction system, taking out the synthesized film, soaking in methanol for 2h, and drying in methanol atmosphere for 24h to obtain UiO-66-NH 2 Mixing ZIF-8 matrix membranes, said UIO-66-NH 2 The mass fraction of ZIF-8 is 10wt%.
Example 6
MOF particles are UiO-66-NH 2 And MIL-101, wherein the metal gel is zinc gel, the substrate is Anodic Aluminum Oxide (AAO) substrate, and the synthesized metal-organic framework mixed metal-organic framework matrix film is UIO-66-NH 2 MIL-101 blendZIF-8 matrix membranes were incorporated.
The preparation method comprises the following steps:
(1)UiO-66-NH 2 is prepared from the following steps: uiO-66-NH 2 Prepared by solvothermal synthesis. Zirconium chloride (0.48 g) and 2-amino terephthalic acid (0.372 g) were dissolved in N, N-dimethylformamide (40 mL) and water (0.19 mL) by stirring and sonication. The solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 120 ℃ for 24 hours. After natural cooling, the powder was isolated by centrifugation at 6000rpm for 5 min. Finally, the powder obtained is washed several times with N, N-dimethylformamide and methanol.
(2) Preparation of MIL-101: chromium nitrate nonahydrate (1.2 g), 1, 4-phthalic acid (0.5 g) and hydrofluoric acid solution (0.6 mL) were added to deionized water (15.0 mL) and stirred for 10min. The mixture was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heat treated at 220 ℃ for 8 hours. After crystallization, MILs-101 powder was separated by centrifugation and washed.
(3) Preparation of a catalyst containing UiO-66-NH 2 And zinc gel of MILs-101: zinc acetate (3.467 g) is added into ethanol (10 mL), stirred at a constant temperature of 60 ℃ for 30min, then ethanolamine (1.0 mL) is added, stirred at a constant temperature of 60 ℃ for 20min, and the transparent non-precipitate zinc sol is obtained, and cooled to room temperature for standby. UiO-66-NH 2 (0.0164 g) and MIL-101 (0.0164 g) were added to 1mL of zinc sol, sonicated for 5min, stirred for 5min, and cycled three times to give UiO-66-NH 2 And MIL-101 is uniformly dispersed in the zinc sol. After uniform dispersion, 2-methylimidazole (0.519 g) was added and stirred rapidly for several minutes to give a solution containing UiO-66-NH 2 And MIL-101 zinc gel.
(4) Synthesis of UiO-66-NH 2 MIL-101 mixed ZIF-8 matrix membrane: taking the UiO-66-NH containing product obtained in the step (3) 2 And 200uL zinc gel of MIL-101 particles are spin-coated on an AAO substrate, dried at 120 ℃ for 25 hours, and after the reaction system is naturally cooled, the synthesized film is taken out, soaked in solvent methanol for 2 hours and dried for 24 hours in the methanol atmosphere, so as to obtain the UiO-66-NH 2 MIL-101 mixed ZIF-8 matrix membrane, said UIO-66-NH 2 MIL-101 accounts for 20wt% of ZIF-8.
Comparative example (original ZIF-8 film without MOF particles added)
The metal gel is zinc gel, the substrate is Anodic Aluminum Oxide (AAO), and the synthesized metal organic framework membrane is a ZIF-8 membrane.
The preparation method comprises the following steps:
(1) Preparing zinc gel: zinc acetate (3.467 g) is added into ethanol (10 mL), stirred at a constant temperature of 60 ℃ for 20min, then ethanolamine (1.0 mL) is added, stirred at a constant temperature of 60 ℃ for 20min for reaction, and transparent non-precipitate zinc sol is obtained and cooled to room temperature for standby. 2-methylimidazole (0.519 g) was added to 1mL of zinc sol and stirred rapidly for several minutes to give a zinc gel.
(2) Synthesis of ZIF-8 membrane: and (3) taking 200uL of zinc gel obtained in the step (1), spin-coating on an AAO substrate, drying at 120 ℃ for 25 hours, cooling the reaction system to room temperature, taking out the synthesized film, soaking the film in solvent methanol for 2 hours, and drying the film in methanol atmosphere for 24 hours to obtain the ZIF-8 film.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (14)
1. The synthesis method of the mixed metal organic framework film is characterized by comprising the following steps of:
(1) Preparing metal organic framework particles: adding metal salt A and organic ligand A into solvent A, mixing uniformly to obtain synthetic solution, carrying out solvothermal reaction on the synthetic solution, naturally cooling after the reaction is finished, washing and drying to obtain metal-organic framework particles;
(2) Preparing mixed metal gel: adding metal salt B into a solvent B, stirring and dispersing uniformly at 30-80 ℃, then adding a chelating agent, continuing to stir and react for 10-80 min at constant temperature to obtain metal sol, adding metal organic framework particles into the obtained metal sol, uniformly mixing, cooling to room temperature, adding an organic ligand B, and stirring uniformly to obtain mixed metal gel containing the metal organic framework particles;
(3) Synthesizing a mixed metal organic framework film: and (3) coating the mixed metal gel containing the metal-organic framework particles obtained in the step (2) on a substrate, then carrying out heat treatment at 60-250 ℃ for 12-48h, naturally cooling to room temperature, taking out the synthesized film, soaking the synthesized film in a solvent C, and drying to obtain the mixed metal-organic framework film.
2. The method for synthesizing a mixed metal organic framework film according to claim 1, characterized in that:
the metal element in the metal salt A in the step (1) is one of Zn, al, fe, cu, ti, cr, co, ni, mg, zr, nb, mo, mn, sm, gd; the metal salt A is nitrate, chloride, carbonate, sulfate or acetate of metal;
the organic ligand A in the step (1) is one of 2-imidazole formaldehyde, 2-methylimidazole, 4-bromoimidazole, imidazole, benzimidazole, terephthalic acid, trimesic acid, 2-amino terephthalic acid and 1, 4-phthalic acid;
the ratio of the amount of the metal salt A to the organic ligand A in step (1) is 1: 0.5-8;
the solvent A in the step (1) is one of a solvent D, a mixed solution of the solvent D and water and a mixed solution of hydrofluoric acid and water, wherein the solvent D is at least one of methanol, N-dimethylacetamide, N-diethylformamide, N-dimethylformamide, octanol and ethanol;
the solvothermal reaction in the step (1) is to heat treat the mixture for 6 to 72 hours at the temperature of 40 to 300 ℃ in a stainless steel autoclave lined with polytetrafluoroethylene.
3. The method for synthesizing a mixed metal organic framework film according to claim 2, characterized in that:
the ratio of the amount of the metal salt A to the organic ligand A in step (1) is 1: 1-2.
4. The method for synthesizing a mixed metal organic framework film according to claim 1, characterized in that:
the metal element in the metal salt B in the step (2) is one of Zn, al, fe, cu, ti, cr, co, ni, mg, zr, nb, mo, mn, sm, gd; the metal salt B is nitrate, chloride, carbonate, sulfate or acetate of metal;
the solvent B in the step (2) is a derivative of monohydric alcohol, dihydric alcohol and alcohols;
the chelating agent in the step (2) is one of ethanolamine, ethylenediamine, diethanolamine, triethanolamine, 2-aminoethanol, triethylamine, diethylenetriamine or ammonia water;
the organic ligand B in the step (2) is at least one of 2-imidazole formaldehyde, 2-methylimidazole, 4-bromoimidazole, imidazole, benzimidazole, terephthalic acid and trimesic acid.
5. The method for synthesizing a mixed metal organic framework film according to claim 4, characterized in that:
the solvent B in the step (2) is one of ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, ethylene glycol ethyl ether or ethylene glycol methyl ether;
the chelating agent in the step (2) is one of ethylenediamine, ethanolamine or ammonia water.
6. The method for synthesizing a mixed metal organic framework film according to claim 1, characterized in that:
the volume consumption of the solvent B in the step (2) is 0.5-50 mL/g based on the mass of the metal salt B;
the ratio of the amount of chelating agent to the amount of metal salt B material described in step (2) is 1: 0.5-8;
the ratio of the amounts of the substances of the metal salt B to the organic ligand B in step (2) is 1: 0.5-12.
7. The method for synthesizing a mixed metal organic framework film according to claim 6, characterized in that:
the volume consumption of the solvent B in the step (2) is 2-22 mL/g based on the mass of the metal salt B;
the ratio of the amount of chelating agent to the amount of metal salt B material described in step (2) is 1: 1-3;
the ratio of the amounts of the substances of the metal salt B to the organic ligand B in step (2) is 1: 1-5.
8. The method for synthesizing a mixed metal organic framework film according to claim 1, characterized in that:
the metal-organic framework particles in the step (2) are at least one of the metal-organic framework particles prepared in the step (1);
the dosage of the metal organic framework particles in the step (2) satisfies that the mass ratio of the metal organic framework particles to the metal gel generated metal organic framework particles is 0-50%, and is not 0.
9. The method for synthesizing a mixed metal organic framework film according to claim 8, characterized in that:
the dosage of the metal organic framework particles in the step (2) satisfies that the mass ratio of the metal organic framework particles to the metal gel generated metal organic framework particles is 0-20%, and is not 0.
10. The method for synthesizing a mixed metal organic framework film according to claim 1, characterized in that:
the substrate in the step (3) is in a flat plate type, a tubular type or a hollow fiber type;
the substrate in the step (3) is made of polypropylene, polyethylene, alumina, titanium dioxide, copper, polytetrafluoroethylene, polyimide, polyether ether ketone, polyvinylidene fluoride, polyacrylonitrile, polysulfone, polyether sulfone, cellulose or zinc.
11. The method for synthesizing a mixed metal organic framework film according to claim 10, characterized in that:
the substrate in the step (3) is made of polysulfone, polyethersulfone, anodized aluminum, polyvinylidene fluoride, polyetherimide or polyacrylonitrile.
12. The method for synthesizing a mixed metal organic framework film according to claim 1, characterized in that:
in the step (3), the solvent C is at least one of methanol, N-dimethylacetamide, N-diethylformamide, N-dimethylformamide, octanol and ethanol.
13. A mixed metal organic framework film prepared according to the method of any one of claims 1-12.
14. Use of the mixed metal organic framework membrane according to claim 13 for gas separation and purification.
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| CN104959044A (en) * | 2015-06-30 | 2015-10-07 | 浙江工业大学 | Method for synthesizing metal organic framework film |
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| CN110052183A (en) * | 2019-04-16 | 2019-07-26 | 暨南大学 | A kind of method that collosol and gel coating combines vapour deposition process to prepare MOF film |
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| CN106215716A (en) * | 2016-08-20 | 2016-12-14 | 齐齐哈尔医学院 | A kind of novel bimetallic organic framework film with high efficiency hydrogen separating property |
| CN110026097A (en) * | 2019-03-29 | 2019-07-19 | 浙江工业大学 | A kind of preparation method of PIM-1@MOFs/ polymer compounding permeation vaporizing film |
| CN110052183A (en) * | 2019-04-16 | 2019-07-26 | 暨南大学 | A kind of method that collosol and gel coating combines vapour deposition process to prepare MOF film |
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